JP3334938B2 - Curable composition and sealing material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition and a sealing material, and more particularly to (A) a hydrocarbon-based compound containing at least two hydrosilyl groups in a molecule and having a molecular weight of 30,000 or less. Curing agent (B) Saturated hydrocarbon polymer containing at least one alkenyl group in the molecule and having a molecular weight of 100,000 or less (C) Hydrosilylation catalyst (D) Less of epoxy group, hydroxyl group and carboxyl group
At least one polar functional group and an alkenyl group or hydroxy group;
An adhesion-imparting agent comprising a compound having both of a ril group, and
And / or curing for epoxy resin and non-amine type epoxy resin
The present invention relates to a curable composition comprising, as an essential component, an adhesion-imparting agent comprising a mixture of agents, and a sealing material obtained by curing the composition.

[0002]

2. Description of the Related Art Conventionally, various sealing materials have been used in the construction, automobile, electric fields, etc., for bonding between the same or different materials or for reinforcing and replenishing during assembly processing. So far, various materials having different curing modes and different main chain structures have been proposed according to each application. However, conventionally used sealing materials include (1) high weather resistance, (2) high heat resistance, (3) quick curing, (4) low moisture permeability, and (5) inorganic and organic materials. There was no material having the same properties as adhesiveness, and there was no material that also considered (6) one-pack stability.

[0003] For example, an addition-curable silicone-based sealing material satisfies the properties (1), (2), (3), (5) and, in some cases, (6).
In the absence of the property (4), when used as a sealing agent, anxiety factors such as peripheral contamination have been observed. Further, the material having a saturated hydrocarbon polymer as the main chain disclosed in JP-A-1-198673 also does not satisfy the above characteristic (3) because it is a condensation-curable system.
Therefore, in order to impart the characteristic (3) to the technique disclosed in JP-A-1-198673, conversion to an addition-type curing system was simply attempted. However, silane coupling such as aminosilane which could be used in a condensation-type curing system was attempted. The agent induced cure inhibition and resulted in loss of property (5).

[0004] The object of the present invention, in view of the current situation at hand,
An object of the present invention is to obtain a curable composition and a sealing material which have the various characteristics (1) to (6) and have excellent mechanical characteristics.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve this object, and as a result, have adopted a curing method different from the technique described in the above-mentioned JP-A-1-198673. And (5) adhesion to inorganic materials,
(6) A technique that satisfies the properties of one-pack type was also found.
Thereby, a curable composition that can achieve the above object,
In addition, a sealing material was obtained, and the present invention was completed.

That is, the present invention relates to (A) a hydrocarbon-based curing agent having at least two hydrosilyl groups in the molecule and having a molecular weight of 30,000 or less; (B) containing at least one alkenyl group in the molecule. A saturated hydrocarbon polymer having a molecular weight of 100,000 or less (C) a hydrosilylation catalyst (D) a small number of epoxy groups, hydroxyl groups and carboxyl groups
At least one polar functional group and an alkenyl group or hydroxy group;
An adhesion-imparting agent comprising a compound having both of a ril group, and
And / or curing for epoxy resin and non-amine type epoxy resin
The present invention relates to a curable composition containing an adhesiveness-imparting agent consisting of a mixture of components as an essential component, and a sealing material obtained by curing the composition. The present invention relates to a curable composition using an improver as an essential component (E) in combination with the above components (A) to (D), and a sealing material obtained by curing the composition.

The structure of the hydrocarbon-based curing agent containing a hydrosilyl group, which is the component (A) of the present invention, is not particularly limited, but the formula (I) RX _a (I) (where X is at least one hydrosilyl group) R is a monovalent to tetravalent hydrocarbon group having 2 to 150 carbon atoms, and a is 1 to 4
An integer selected from )), A hydrocarbon-based curing agent containing a hydrosilyl group having a molecular weight of 30,000 or less can be suitably used.

In the formula (I), X represents a group containing at least one hydrosilyl group, and specific examples include -Si (H) _n (CH ₃ ) _3-n and -Si (H ) _N (C ₂ H
₅ ) _3-n , -Si (H) _n (C ₆ H ₅ ) _3-n , (n = 1
3) a hydrosilyl group containing only one silicon atom, such as -SiH ₂ (C ₆ H ₁₃ );

[0009]

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A hydrosilyl group containing two or more silicon atoms, such as

[0011]

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[0012]

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[0013]

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And the like. Hydrosilyl groups derived from various kinds of chain, branched and cyclic polyvalent hydrogen siloxanes are exemplified. Among the above various hydrosilyl groups, the hydrosilyl group constitutes the hydrosilyl group in that the compatibility of the hydrosilyl group-containing hydrocarbon-based curing agent, which is the component (A) of the present invention, with various organic polymers is less likely to be impaired. The molecular weight of the portion is desirably 500 or less,
In consideration of the reactivity of the hydrosilyl group, the following compounds are preferred.

[0015]

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[0016]

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In the formula (I), R represents 1 to 150 carbon atoms.
Represents a tetravalent hydrocarbon group. The number of hydrosilyl groups contained in the formula (I) may be at least two in one molecule, but is preferably 2 to 15, and particularly preferably 3 to 12. In the case where the composition of the present invention is cured by a hydrosilylation reaction, if the number of the hydrosilyl groups is less than 2, curing is slow and curing failure often occurs. When the number of the hydrosilyl groups is more than 15,
The stability of the curing agent (A) becomes poor, and a large amount of hydrosilyl groups remains in the cured product even after curing, which causes voids and cracks.

The method for producing the hydrosilyl group-containing hydrocarbon-based curing agent which is the component (A) of the present invention is not particularly limited, and any method may be used. For example, (i) a hydrocarbon-based curing agent having a Si—Cl group in a molecule is LiAl
A method of reducing the Si—Cl group in the curing agent to a Si—H group by treating with a reducing agent such as H ₄ or NaBH ₄ , (ii) a hydrocarbon compound having a functional group X in the molecule and a molecule (Iii) a method of reacting a compound having a functional group Y and a hydrosilyl group simultaneously reacting with the functional group X, and (iii) at least 2
And a method of selectively hydrosilylating a polyhydrosilane compound having two hydrosilyl groups so that the hydrosilyl groups remain in the molecule of the hydrocarbon compound even after the reaction.

Of the above methods, the method (iii) can be suitably used because the manufacturing process is generally simple. In this case, two or more hydrosilyl groups of some polyhydrosilane compounds may react with the alkenyl group of the hydrocarbon compound to increase the molecular weight. Such a hydrocarbon compound may be used as the component (A). No problem.

The component (B) used in the present invention has a molecular weight of 10,000 having at least one alkenyl group in the molecule.
It is a saturated hydrocarbon polymer having 0 or less. Here, the saturated hydrocarbon polymer is a concept meaning a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring,
It means that the repeating unit constituting the main chain excluding the alkenyl group is composed of a saturated hydrocarbon. Also,
An alkenyl group refers to a group having one carbon-carbon double bond. In the present invention, the component (B) preferably has 1 to 10 alkenyl groups in one molecule.

The polymer constituting the skeleton of the saturated hydrocarbon polymer as the component (B) is (1) ethylene, propylene,
-Polymerizing an olefinic compound having 1 to 6 carbon atoms such as butene and isobutylene as a main monomer,
(2) It can be obtained by a method such as homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing the olefin compound and the diene compound and then hydrogenating the compound. In terms of easy introduction of functional groups into the polymer, easy control of molecular weight, and increase in the number of terminal functional groups, isobutylene-based polymers, hydrogenated polybutadiene-based polymers, or hydrogenated polyisoprene-based polymers Preferably it is.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, and the monomer unit having copolymerizability with isobutylene is preferably 50% ( %, The same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less.

Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes and the like. Specific examples of such a copolymer component include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, and 4-methyl-
1-pentene, hexene, vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, pt-butoxystyrene, p-hexenyloxystyrene, p-allyloxystyrene, p-hydroxy Styrene, β-pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3
-Divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallylmethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and the like.

In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, similarly to the case of the above-mentioned isobutylene-based polymer, in addition to the monomer unit serving as the main component,
Other monomer units may be contained. In the present invention, the saturated hydrocarbon polymer used as the component (B) includes butadiene, isoprene, 1,13-tetradecadiene, 1,9-decadiene, 1,5 as long as the object of the present invention is achieved. -A small amount, preferably 10% or less, of a monomer unit such as a polyene compound such as hexadiene, in which a double bond remains after polymerization, may be contained.

The number average molecular weight of the above-mentioned saturated hydrocarbon polymer, preferably isobutylene polymer, hydrogenated polyisoprene or hydrogenated polybutadiene polymer is 500 to 1000.
It is preferably about 00, especially 1000 to 4000
It is preferable that the material has a liquid property of about 0 to a fluidity from the viewpoint of easy handling. About the method of introducing an alkenyl group into the saturated hydrocarbon polymer of the component (B),
Although various proposals can be used, they can be broadly classified into a method of introducing an alkenyl group after polymerization and a method of introducing an alkenyl group during polymerization.

As a method for introducing an alkenyl group after the polymerization, for example, a hydroxyl group at a terminal, main chain or side chain may be
After forming a group such as ONa or —OK, general formula (2) CH ₂ ＣＨCH—R ³ —Y (2) wherein Y is a halogen atom such as a chlorine atom or an iodine atom, and R ³ is —R ⁴ — ^{, -R 4 -OC (= O)} - or -R
^{4 -C (= O) - (} R 4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group specific examples, a cycloalkylene group, an arylene group, and aralkylene group) represented by A divalent organic radical,

[0027]

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(R ⁵ is particularly preferably a divalent group selected from the group consisting of hydrocarbon groups having 1 to 10 carbon atoms). A polymer is produced. The terminal hydroxyl groups of hydroxy-terminated saturated hydrocarbon polymer as a method for the oxy metal group, Na, K of such alkali metal: NaH metal hydride such as; NaOCH ₃ in such a metal alkoxide; sodium hydroxide, such as potassium hydroxide caustic And the like.

In the above method, a saturated hydrocarbon polymer having a terminal alkenyl group having substantially the same molecular weight as the polymer having a terminal hydroxy saturated hydrocarbon used as a starting material can be obtained, but a polymer having a higher molecular weight is desired. In such a case, before reacting the organic halogen compound of the general formula (2), two or more halogen atoms are contained in one molecule such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether and the like. The molecular weight can be increased by reacting with a polyvalent organic halogen compound, and then by reacting with an organic halogen compound represented by the general formula (2),
A hydrogenated polybutadiene-based polymer having a higher molecular weight and having an alkenyl group at a terminal can be obtained.

Specific examples of the organic halogen compound represented by the general formula (2) include, for example, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl ( Chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy)
Examples include, but are not limited to, benzene and allyloxy (chloromethyl) benzene. Of these, allyl chloride is preferred because it is inexpensive and easily reacts.

The method of introducing an alkenyl group into an isobutylene-based polymer having a covalent Cl group is not particularly limited. For example, a method of performing a Friedel-Crafts reaction of various alkenyl phenyl ethers with a Cl group, A method of performing a substitution reaction between an allyltrimethylsilane or the like and a Cl group in the presence of a Lewis acid, and a method of performing a Friedel-Crafts reaction between various phenols and a Cl group to introduce a hydroxyl group, and further introducing the alkenyl group. The method of using together etc. is mentioned.

As a method for introducing an alkenyl group during the polymerization, for example, a compound having a halogen atom as an initiator and a chain transfer agent, wherein a carbon atom to which the halogen atom is bonded to an aromatic ring carbon is used. And / or using a compound having a halogen atom, wherein the carbon atom to which the halogen atom is bonded is a tertiary carbon atom, and using a Lewis acid as a catalyst to convert a cationic polymerizable monomer containing isobutylene into a cation. For the polymerization, a method for producing an allyl-terminated isobutylene-based polymer by adding allyltrimethylsilane to the polymerization system,
A method for producing an isobutylene-based polymer having an alkenyl group at the terminal of a main chain or a side chain by adding a non-conjugated diene such as -decadiene or an alkenyloxystyrene such as p-hexenyloxystyrene to a polymerization system. No.

The Lewis acid used as the cationic polymerization catalyst is a Lewis acid represented by MX'n (M is a metal atom and X 'is a halogen atom), for example, BCl ₃ , E
t ₂ AlCl, EtAlCl ₂ , AlCl ₃ , SnCl
₄ , TiCl ₄ , VCl ₅ , FeCl ₃ , BF _{3 and the} like, but are not limited thereto. Among these Lewis acids, BCl ₃ , SnCl ₄ , BF _{3 and the} like are preferable, and TiCl ₄ is more preferable. The amount of the Lewis acid to be used is preferably 0.1 to 10 times, more preferably 2 to 5 times, the number of moles of the initiator chain transfer agent.

The ratio of the hydrosilyl group to the alkenyl group of the component (A) and the component (B) produced as described above is preferably 0.2 to 5.0, more preferably 0.4 to 2.0, in a molar ratio.
5 is particularly preferred. When the molar ratio is less than 0.2,
When the composition of the present invention is cured, only a cured product with insufficient curing and tackiness and low strength is obtained, and when the molar ratio is larger than 5.0, active hydrosilyl groups remain in the cured product even after curing. Since a large amount remains, cracks and voids are generated, and a uniform and strong cured product tends not to be obtained.

The hydrosilylation catalyst which is the component (C) of the present invention is not particularly limited, and any catalyst can be used. Specifically, chloroplatinic acid, a simple substance of platinum,
Solid platinum supported on a carrier such as alumina, silica or carbon black; platinum-vinylsiloxane complex {for example, Pt _n (ViM
e ₂ SiOSiMe ₂ Vi) _m , Pt [(MeViSi
O) ₄ ] _m }; platinum-phosphine complex {for example, Pt
(PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {for example, Pt [P (OPh ₃ ] ₄ , Pt
[P (OBu) ₃ ] ₄ } (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers), Pt (acac) ₂ , In addition, Ashby (Ash
by) US Patents 3,159,601 and 3,159,662
No. 3220 to Lamoreaux, a platinum-hydrocarbon complex described in US Pat.
Also included are the platinum alcoholate catalysts described in 972.

Examples of the catalyst other than the platinum compound include Rh / Al ₂ O ₃ . These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt (acac) _{2 and the} like are preferable. The amount of the catalyst is not particularly limited, but is preferably in the range of 10 ^-1 to 10 ^-8 mol per ¹ mol of the alkenyl group in the component (B). Preferably 10 ^-3 to 10 ^-6 mo
It is good to use in the range of l.

The following compounds are exemplified as the adhesion-imparting agent which is the component (D) of the present invention. That is, a compound having a polar functional group such as an epoxy group, a hydroxyl group, a carboxyl group, or the like, and a functional group that participates in an addition-type curing system such as an alkenyl group, a hydrosilyl group, or the like and can be incorporated into a main chain during curing, or And a mixture of an epoxy resin and a non-amine type epoxy resin curing agent which can be incorporated into the main chain at the time of curing.

Here, the main chain refers to a molecule generated when the curable composition of the present invention is cured, and the component (D) reacts with at least the components (A) and / or (B), Incorporated into the molecule. In the above compound, the polar functional group is involved in an addition-type curing system such as an alkenyl group / hydrosilyl group / the like, and the addition-type curing system is the component (A) and / or (B) in the present invention itself. Or a compound having an independent alkenyl group and / or hydrosilyl group. In the latter case, the resulting compound must undergo a binding reaction with at least the (A) and / or (B) components.

The epoxy group, hydroxyl group,
Polar functional groups such as carboxyl group etc. are the same molecule and / or
Alternatively, the heterogeneous molecule can have one or more polar functional groups. Specific examples of the compound include a hydroxyl group / alkenyl group represented by 9-decen-1-ol, an epoxy group / alkenyl group represented by allyl glycidyl ether, and a carboxyl group / alkenyl represented by 10-undecylenic acid. And compounds having a polar functional group such as a group. Further, the component (A) used in the present invention, a hydrocarbon-based curing agent containing at least two or more hydrosilyl groups in the molecule and having a molecular weight of 30,000 or less, or any chain other than the component (A) Obtained by a partial hydrosilylation reaction of a polyvalent hydrogensiloxane having a branched or cyclic structure with a compound having a polar functional group / alkenyl group such as an epoxy group, a hydroxyl group, a carboxyl group, etc. Epoxy group, hydroxyl group,
Compounds having both a polar functional group such as a carboxyl group and the like / hydrosilyl group are exemplified. The conditions for the above-mentioned partial hydrosilylation reaction are not particularly limited, and may be used in advance after heating and mixing in the presence of a hydrosilylation catalyst to complete the reaction, purification and isolation, or
What is simply mixed at room temperature without solvent may be used as it is. However, in order for the compound to participate in the addition-type curing system by the hydrosilylation reaction with the alkenyl group of the component (B) and to be incorporated into the main chain during curing, one or more hydrosilyl groups must remain in the molecule. In addition, in order to participate in an addition-type curing system by a hydrosilylation reaction with the hydrosilyl group of the component (A) and to be incorporated into the main chain during curing, one or more alkenyl groups remain in the molecule. It is necessary to let And the compound of
The binding reaction with both the component (A) and the component (B) may be performed.

Examples of the polyvalent hydrogen siloxane other than the component (A) include, for example, LS-8600 for a cyclic compound.
[Shin-Etsu Co., Ltd.] Examples of various linear hydrogen polysiloxanes include straight-chain ones. Further, among the above-mentioned mixtures exemplified by the adhesion-imparting agent as the component (D) of the present invention, that is, the epoxy compound and the curing agent for the non-amine type epoxy resin, the epoxy compound is, for example, epichlorohydrin-bisphenol A type epoxy. Resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct , P-oxybenzoic acid-glycidyl ether ester type epoxy resin, III-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N,
N-diglycidylaniline, N, N-diglycidyl-o
Glycidyl ethers of polyhydric alcohols such as toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin,
Examples thereof include an epoxidized product of an unsaturated polymer such as a hydantoin type epoxy resin and a petroleum resin. However, the present invention is not limited to these, and any generally known epoxy resin can be used. Among these epoxy resins, the formula:

[0041]

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Those containing at least two epoxy groups in the molecule are preferred, and bisphenol A epoxy resins, novolak epoxy resins, and various alicyclic epoxy resins are more preferred. Further, as a curing agent for a non-amine type epoxy resin, for example, a boron trifluoride compound: phthalic anhydride, hexahydrophthalic anhydride,
Carboxylic anhydrides such as tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecinyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .: alcohols: phenols: carboxylic acids: aluminum isopropylate, aluminum sec-butylate, Aluminum tert-butylate, aluminum tris (ethyl acetoacetate), aluminum trishexafluoroacetylacetonate, aluminum trisethylacetoacetate, aluminum tris (n-propylacetoacetate), tris (iso-)
Propyl acetoacetate) aluminum, tris (n
Aluminum complexes such as -butyl acetoacetate) aluminum, tris salicylaldehyde aluminum, tris (2-ethoxycarbonyl phenolate) aluminum, tris (acetylacetonato) aluminum, etc .:

The above aluminum complex may be used in combination with diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiacetoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, diphenylvinylethoxysilane, etc. Aluminum complex / alkoxysilane mixture which is a mixture with alkoxysilane: Aluminum complex / organic silanol mixture which is a mixture of the above aluminum complex and an organic silanol such as diphenyldisilanol, diphenylmethylsilanol, trimethylsilanol, triphenylsilanol and the like: Tetramethyl zirconate, tetraethyl zirconate, tetraisopropyl zirconate, tetra-n-butylzyl Titanate, tetra isobutyl zirconate, tetra -tert- butyl zirconate, tetrakis (OKI The Rick A Sid) zirconium, tetrakis (acetylacetonate) zirconium, tetrakis (n-
Compounds such as zirconium complexes such as propylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, and tetrakis (salicylaldehyde) zirconium can be exemplified.

Among these non-amine type epoxy resin curing agents, a mixture of an aluminum complex / alkoxysilane and a mixture of an aluminum complex / organic silanol are preferable in that the curing of the epoxy resin upon heating is fast. The amount of the curing agent for the non-amine type epoxy resin varies depending on the type of the epoxy resin and the curing agent. However, 1 to 100 parts (parts by weight, hereinafter the same) of the epoxy resin is used depending on the purpose. It may be used in the range of parts.

In the present invention, curing agents for epoxy resins generally used for curing epoxy resins, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, meta- Xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,
The use of amines such as 4,6-tris (dimethylaminomethyl) phenol and the like: amine-based epoxy resin curing agents such as tertiary amine salts can be used in the present invention (A),
It is not preferable because curing of the components (B) and (C) by the hydrosilylation reaction is inhibited. In the present invention, the ratio (weight ratio) of [(A) component + (B) component + (C) component] / [(D) component] may be properly used depending on the purpose of use. However, for example, if it is only desired to provide [Component (A) + component (B) + component (C)] with adhesiveness to various base materials, 100 / 0.1 to 100/20
(Weight ratio) is preferable, and 100/10 to 100/200 (weight ratio) is more preferable in order to further improve the mechanical strength.

Further, in the present invention, when a mixture of the above epoxy resin and a curing agent for a non-amine type epoxy resin among the adhesion imparting agents of the component (D) is used, only the adhesion to various substrates is imparted. In addition, there is an effect that the restoration rate of the cured product after the curing in the compression / tensile durability test is improved. Further, in the present invention, it is desirable to use a storage stability improver as an essential component (E) as necessary.

Examples of the storage stability improver include 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, BHT, butylhydroxyanisole, vitamin E, 2- (4 -Morphodinyldithio) benzothiazole, 3-methyl-1-
Controlling the catalytic activity of the component (C) such as buten-3-ol, 3-methyl-1-butyl-3-ol, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate only during storage at room temperature Is desirable.
When the storage stability improver is used, the amount of catalyst 1
0.1 to 1000 mol, preferably 1 to 1000 mol
100 mol. When the amount of the storage stability improver exceeds the upper limit of the above-mentioned amount, not only does curing delay occur, but also curing failure occurs, and the physical properties required for the cured product cannot be satisfied. Conversely, if the amount of the storage stability improver is below the lower limit of the above amount, the object of improving the storage stability of the composition cannot be achieved.

(A), (B), (C), (D) of the present invention
In some cases, if the component (E) is mixed and cured, a uniform cured product having excellent deep curability can be obtained without causing a phenomenon such as foaming. The curing conditions are not particularly limited, but are generally 0 to 200 ° C, preferably 30 to 15 ° C.
It is preferred to cure at 0 ° C. for 10 seconds to 4 hours. Especially 80-1
At a high temperature of 50 ° C., one that cures in a short time of about 10 seconds to 1 hour can be obtained. The properties of the cured product depend on the main chain skeleton, molecular weight, etc. of the components (A) and (B) used, but can be prepared from rubbery to resinous. In addition, the ratio of the total of the four essential components (A), (B), (C) and (D) to the total composition at the time of preparing the cured product by adding the blend is 10% or more, and more preferably 30% or more.
% Or more, and various components are added as necessary.

Examples of the components to be added include, for example, a physical property adjuster for adjusting the tensile properties of the resulting cured product, a plasticizer, a filler, an ultraviolet absorber, a lubricant and a pigment. As the plasticizer, a commonly used plasticizer can be used, but a plasticizer having good compatibility with the saturated hydrocarbon polymer used in the present invention is preferable. Specific examples of the plasticizer include, for example, polybutene, hydrogenated polybutene, α-methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl, partially hydrogenated Hydrocarbon compounds such as phenyl, paraffin oil, naphthenic oil, and atactic polypropylene, preferably hydrogenated polybutene containing no unsaturated bond, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, and atactic polypropylene;
Dibutyl phthalate, diheptyl phthalate, di (2-
A phthalic acid ester adhesive such as ethylhexyl) phthalate, butylbenzyl phthalate, and butylphthalylbutyl glycolate, a silane coupling agent, and other compounds can be used. Specific examples of such a compound include a phenol resin, an epoxy resin, an aminosilane compound such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, an epoxysilane compound, and a cumarone-indene resin. Rosin ester resin, terpene-phenol resin, α-methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanates, aromatic polyisocyanate, and the like.

Specific examples of the filler include, for example, asbestos, glass fiber, carbon fiber, mica, graphite, diatomaceous earth, clay, fume silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate,
Clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint powder, zinc dust and the like can be mentioned. Among these fillers, sedimentable silica, fumed silica, fillers having thixotropic properties such as carbon black, calcium carbonate, titanium oxide,
Talc is preferred. When a filler is used, the amount is 10 parts per 100 parts of the saturated hydrocarbon polymer (B).
The amount is preferably from 500 to 500 parts, more preferably from 20 to 300 parts.

When the curable composition of the present invention is used as a sealing material, the substrate to which the curable composition is applied includes inorganic glass, organic glass, aluminum, iron, reinforced plastic,
It may be made of wood, mortar, concrete, etc., and exhibits stable adhesiveness to these substrates for a long period of time. Then, it rapidly cures under heating and becomes a rubber-like material having excellent mechanical properties as a sealing material.

The rubbery material thus obtained has low moisture permeability and good weather resistance, weather resistance, heat resistance and electrical insulation. Further, the sealing material of the present invention has good storage stability and is stable for a long time in a low temperature state, so that it can be used as a one-part sealing agent having good workability.

Further, a fluid having appropriate viscosity and structural viscosity (thixotropic property) at normal temperature can be obtained, and workability and sprayability are good. Also, when using the sealing material of the present invention to produce a double glazing,
The line speed can be increased due to the rapid curing, and there is an advantage that the conventional double seal can be replaced with a single seal.

Of course, it can be used for conventional double-sealed double-glazed glass, and can also be used as a two-part sealing material. Further, the composition of the present invention is quickly cured by heating, and the cured product becomes a rubber-like elastic body. As a result, a problem such as cracking of the chip or cutting of the bonding wire hardly occurs due to the thermal stress caused by the thermal stress, and a highly reliable semi-moving part is manufactured. Furthermore, the sealing performance is, for example, that the moisture permeability coefficient is 1 × 10 ⁻¹¹ g · cm / cm ² · sec.
・ Excellent moisture barrier property of about cmHg, excellent adhesion to aluminum substrate of about 6kg / 25mm by T-peeling, and melting is seen on the surface even under severe conditions such as 300 days at 130 ° C. As is evident from the excellent electrical properties represented by the excellent heat resistance and the excellent dielectric constant of about 2.44, a very excellent material is provided.

When the composition of the present invention is applied as a sealing resin, potting may be carried out in the same manner as a conventional epoxy resin sealing resin.

[0056]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Production Example 1 A stirring vessel, a three-way cock, and a vacuum line were attached to a 1-liter pressure-resistant glass autoclave, and the polymerization vessel was dried by heating at 100 ° C. for 1 hour while evacuating the vacuum line, and then cooled to room temperature. The pressure was returned to normal pressure with nitrogen using a three-way cock.

Then, while flowing nitrogen from one of the three-way cocks, 40 ml of 1,1-dichloroethane, which was a main solvent dried by calcium hydride treatment, was introduced into the autoclave using a syringe. Subsequently, 5 mmol of distilled and purified allyltrimethylsilane was added, and TCC was further added.
(Compound A below) 10 ml of 1,1-dichloroethane solution in which 2 mmol was dissolved was added.

Next, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 7 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. It was immersed in a dry ice-acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the interior of the reactor was depressurized by a vacuum line, and then the needle valve was opened. Isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube. Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks. Further, cooling was continued for 1 hour with stirring.
The temperature was raised to 10 ° C.

Next, 3.2 g (10 mmol) of TiCl ₄ was added from a three-way cock using a syringe to start polymerization, and after 60 minutes, methanol which had been cooled to 0 ° C. or less in advance was added. By doing so, the reaction was completed. Thereafter, the reaction mixture was taken out into an eggplant-shaped flask, and unreacted isobutylene, 1,1-dichloroethane,
Allyltrimethylsilane and methanol were distilled off, the remaining polymer was dissolved in 100 ml of n-hexane, and this solution was repeatedly washed with water until the solution became neutral. Then, the n-hexane solution was concentrated to 20 ml, and the concentrated solution was poured into 300 ml of acetone to precipitate and separate the polymer.

The polymer thus obtained was again
It was dissolved in 00 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene-based polymer. The structure of Compound A is as shown below.

[0061]

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Production Example 2 5 g of the isobutylene-based polymer obtained in Production Example 1 was
After dissolving in 0 ml of n-hexane, adding 2 g of aluminum silicate and stirring at room temperature for 24 hours, the mixture was filtered and n-hexane was distilled off under reduced pressure to obtain an isobutylene-based polymer. Production Example 3 A stirring vessel, a three-way cock and a vacuum line were attached to a 100 ml pressure-resistant glass autoclave, and the polymerization vessel was dried by heating at 100 ° C. for 1 hour while evacuating the vacuum line, and then cooled to room temperature. The pressure was returned to normal pressure with nitrogen using a cock.

Thereafter, while flowing nitrogen from one of the three-way cocks, methylene chloride 4 which is a main solvent dried by calcium hydroxide treatment in an autoclave using a syringe was injected.
0 ml was introduced. Next, 20 mmol of distilled and purified 1,9-decadiene was added, and further a methylene chloride solution (10 ml) in which 3 mmol of tricumyl chloride (TCC) was dissolved was added.

Next, a liquefied gas sampling tube with a needle valve containing 7 g of isobutylene dehydrated by passing through a column focused on barium oxide was connected to a three-way cock. It was immersed in a dry ice-acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the interior of the reactor was depressurized by a vacuum line, and then the needle valve was opened. Isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube. Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks. Further, cooling was continued for 1 hour with stirring, and the temperature inside the polymerization vessel was raised to -30 ° C.

Next, 3.2 g of TiCl ₄ (10 mm
1) was added from a three-way cock using a syringe to start polymerization, and after 60 minutes, methanol, which had been cooled to 0 ° C. or lower in advance, was added to complete the reaction. Thereafter, the reaction mixture was taken out into an eggplant-shaped flask, and unreacted isobutylene, methylene chloride, 1,9-decadiene and methanol were distilled off.
After dissolving in 00 ml of n-hexane, the solution was repeatedly washed with water until the solution became neutral. Thereafter, the n-hexane solution was concentrated to 20 ml, and the concentrated solution was poured into 300 ml of acetone to precipitate and separate the polymer.

The polymer thus obtained was again
It was dissolved in 00 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene-based polymer.

Production Example 4 A three-way cock was attached to a 200-ml pressure-resistant glass container, and the polymerization container was evacuated to 100 by drawing a vacuum in a vacuum line.
The resultant was dried by heating at 1 ° C. for 1 hour, cooled to room temperature, and then returned to normal pressure with nitrogen using a three-way cock. Thereafter, while flowing nitrogen from one of the three-way cocks, a solution prepared by dissolving 1 mmol of tricumyl chloride shown in Chemical Formula 9 in 40 ml of methylene chloride dried by calcium hydride treatment was added to the autoclave using a syringe.

Next, a pressure-resistant glass liquefied gas sampling tube with a needle valve containing 5 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. It was immersed in a dry ice-acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the interior of the reactor was depressurized by a vacuum line, and then the needle valve was opened. Isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube. Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks. Further, cooling was continued for 1 hour with stirring.
Cooled to 70 ° C.

Next, a solution (−30 ° C.) obtained by diluting 10 mmol of tin tetrachloride with 20 ml of methylene chloride was added from a three-way cock using a syringe to start polymerization. When 60 minutes had elapsed, 10 mmol of allyl phenyl ether was added. Was added from a three-way cock using a syringe. Thereafter, the reaction solution was stirred at room temperature for 6 hours, shaken with 100 ml of a saturated aqueous solution of sodium hydrogen carbonate, and then the organic layer was washed with water 1
Washed twice with 00 ml. Concentrate the organic layer to 10 ml,
The polymer was precipitated and separated by adding it to 300 ml of acetone with stirring.

The polymer obtained in this way is 80 m
l-n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene-based polymer. The yield was calculated from the yields of the polymers obtained in Production Examples 1 to 4, and M
by GPC n and Mw / Mn, also a terminal structure ¹ H
-Protons belonging to each structure by NMR (300 MHz) method (aromatic protons derived from initiator: 6.5 to 7.5 ppm, and vinyl protons derived from polymer terminals: 4.5 to 5.9 p)
pm) by measuring and comparing the intensity of the resonance signal. The chlorine content in the polymer was determined by elemental analysis.
Table 1 shows the results.

[0071]

[Table 1]

Production Example 5 50 ml of toluene was added to 300 g of hydrogenated polyisoprene having hydroxyl groups at both terminals (Epol, trade name, manufactured by Idemitsu Petrochemical Co., Ltd.), and the mixture was dehydrated by azeotropic degassing. t-BuO
A solution in which 48 g of K was dissolved in 200 ml of THF was injected. After reacting at 50 ° C. for 1 hour, allyl chloride 4
7 ml was added dropwise over about 30 minutes. 50 ° C after dropping
For 1 hour. After completion of the reaction, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred at room temperature for 30 minutes. About 250
g of allyl-terminated hydrogenated polyisoprene was obtained as a viscous liquid. 300 MHz ¹ H-NMR analysis confirmed that 92% of the terminal had an allyl group introduced. The number of moles of the olefin determined from the iodine value was 0.1046 mol / 100 g. The chlorine content determined by elemental analysis was 0.1% or less.
The viscosity measured by an E-type viscometer was 302 poise (23 ° C.).

* Typical physical properties of Epol (from technical data) Hydroxyl content (meq / g) 0.90 Viscosity (poise / 30 ° C.) 700 Average molecular weight (VPO measurement) 2500 Production Example 6 Stirrer, dropping funnel, thermometer A 300 ml four-necked flask equipped with a three-way cock and a condenser was prepared. Next, under a nitrogen atmosphere,

[0074]

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(LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) 3
1.5 g (0.131 mol) was charged in the flask. Fifty grams of hydrogenated polyisoprene (0.0536 mol of olefin moles) synthesized in Production Example 5 in which 92% of the molecular terminals are allyl groups, 50 ml of toluene, and 1 g of a platinum catalyst solvent (Pt (acac) ₂ ) in 99 g of toluene A solution of 60 μl of toluene dissolved in the dropping funnel was charged. The flask was heated to 70 ° C., and the toluene solution was added dropwise over about 2 hours. After dropping, 80 ° C
At about 5 hours, the remaining allyl groups in the reaction solution were quantified by IR spectroscopy.
It was confirmed that the carbon-carbon double bond at 5 cm ^-1 had disappeared. Next, silica gel (Wako Pure Chemical Industries, Ltd., Wakogel C) was used to remove the catalyst remaining in the reaction system.
-200) was added at room temperature, stirred for 2 hours, and filtered using a flash column. The filtrate was evaporated to remove toluene and excess cyclic polysiloxane, and further degassed under reduced pressure at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The viscosity measured by an E-type viscometer was 514 poise (23 ° C.). The hydrosilyl group in the hydrogenated polyisoprene was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. The peak of the Si- H in NMR spectra of 300MHz and SiC H ₃ and SiC H ₂ -
By comparing the intensities of the peaks with the above, it was found that an average of 1.2 hydrosilyl groups per molecule of the cyclic polysiloxane had reacted. That is, the polymer is a hydrogenated polyisoprene having a molecular terminal represented by the following formula 11 and having a molecular weight partially increased by the cyclic hydrogen polysiloxane.

[0076]

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Production Example 7 Instead of the polymer obtained in Production Example 5, the polymer obtained in Production Example 2 was used, and the amount of the polymer was 50 g and LS-860 was used.
Production was carried out in the same manner as in Production Example 6, except that the amount of 0 was changed to 16 g.

Production Example 8 A 200 ml four-necked flask was equipped with a cooling tube with a three-way cock, a pressure equalizing dropping funnel, a thermometer, a magnetic chip,
A glass stopper was prepared. Under a nitrogen atmosphere, 12.03 g (50 mmo) of the cyclic polysiloxane represented by Chemical formula (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.)
l) and 20 ml of toluene were charged into a flask.
A solution obtained by dissolving 2.76 g (20 mmol) of 1,9-decadiene and 200 μl of a platinum catalyst solution (a solution of 1 g of Pt (acac) ₂ in 99 g of toluene) in 30 ml of toluene was charged into a dropping funnel. The flask was placed in a 50 ° C. oil bath, and the toluene solution was dropped into the flask over 2 hours under a nitrogen atmosphere. 50 ° C after dropping
When the reaction was further performed for 1 hour, the IR spectrum was measured. Since the absorption of the olefin near 1640 cm ^-1 had completely disappeared, the reaction was terminated at this point. The toluene solution after the completion of the reaction was mixed with a saturated aqueous solution of ammonium chloride (100 ml × 2) and exchanged water (100 ml ×
After washing in 1), it was dried over Na ₂ SO ₄ . Na ₂ SO ₄
Was removed by filtration, volatile matter was removed by evaporation, and then degassed at 80 ° C. under reduced pressure to obtain 9.11 g of a colorless and transparent liquid. The hydrosilyl group in the hydrocarbon-based curing agent was confirmed as a strong absorption at 2170 cm ^-1 . In addition, the peak of Si-H and the Si-
By comparing the intensity ratio of the proton with CH ₃ (actually measured value 0.216) and the calculated intensity ratio, the curing agent has, on average, the structure of the following formula (n = 1 (Mw =
998) is 53% and n = 2 (Mw = 1377) is 47
%] Mixture. Calculating the number of Si-H groups per unit weight based on this, 0.769 mol
/ 100 g.

[0079]

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Production Example 9 An equalizing dropping funnel was placed in a 500 ml four-necked eggplant flask.
A thermometer, a stirring propeller, and a three-way cock were provided. Under a nitrogen atmosphere, 20 g (50 g) of the cyclic polysiloxane (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.)
mmol) and 50 ml of toluene were charged into the flask. Allyl glycidyl ether 19 g, platinum-vinylsiloxane complex solution (8.3 × 10 ⁻⁵ mmol / μl) 4
A solution obtained by mixing 00 μl and 50 ml of toluene was charged into the dropping funnel. The flask was placed in a water bath at 15 ° C., and the solution was added dropwise in about 30 minutes while stirring under a nitrogen atmosphere.
Thereafter, stirring at room temperature was further continued for 4 hours. During the dropping, the temperature of the solution in the flask was raised to about 25 ° C. I
The R spectrum confirmed that the absorption of the olefin near 1640 cm ^-1 had disappeared, and the reaction was terminated at this point. For the purpose of stabilizing the reaction product, 100 μl of benzothiazole was added, followed by concentration under reduced pressure at 60 ° C. or lower in vacuo to obtain the desired product.

The structure of the thus obtained adhesiveness-imparting agent was examined by NMR in the same manner as in Production Example 8. As a result, a cyclic polysiloxane having about 2 epoxy groups and about 2 SiH groups per molecule was obtained. Was confirmed. Production Example 10 Into a 500 ml four-necked eggplant flask, a pressure equalizing dropping funnel was prepared.
A thermometer, a stirring propeller, and a three-way cock were provided. Under a nitrogen atmosphere, 50 g of the curing agent synthesized in Production Example 8 and 100 ml of toluene were charged in the flask. Allyl glycidyl ether 22 g, platinum-vinylsiloxane complex solution (8.3 × 10 ⁻⁵ mmol / μl) 500 μ
l and 100 ml of toluene were charged into a dropping funnel. The flask was placed in a water bath at 15 ° C., and the above solution was added dropwise in about 30 minutes with stirring under a nitrogen atmosphere, and then stirring at room temperature was continued for 4 hours. At the time of dropping, the temperature of the solution in the flask rose to about 28 ° C. The IR spectrum confirmed that the absorption of the olefin near 1640 cm ^-1 had disappeared, and the reaction was terminated at this point. For the purpose of stabilizing the reaction product, 100 μl of benzothiazole was added, followed by concentration under reduced pressure at 60 ° C. or lower in vacuo to obtain the desired product.

The structure of the thus obtained adhesiveness-imparting agent was examined by NMR in the same manner as in Production Examples 8 and 9. Compounds having about 3 epoxy groups and about 3 SiH groups in one molecule were obtained. Was confirmed. If the number of SiH groups per unit weight is calculated based on this, 0.382 mol / 10
It was 0 g. Production Example 11 Equilibrium dropping funnel was placed in a 500 ml four-necked eggplant flask,
A thermometer, a stirring propeller, and a three-way cock were provided. Under a nitrogen atmosphere, 50 g of the curing agent synthesized in Production Example 8 and 100 ml of toluene were charged in the flask. 9-
30 g of decene-1-ol, 500 μl of a platinum-vinylsiloxane complex solution (8.3 × 10 ⁻⁵ mmol / μl),
A solution obtained by mixing 100 ml of toluene was charged into the dropping funnel. The flask was placed in a water bath at 15 ° C., and the above solution was added dropwise in about 30 minutes with stirring under a nitrogen atmosphere, and then stirring at room temperature was continued for 4 hours. At the time of dropping, the temperature of the solution in the flask rose to about 22 ° C. The IR spectrum confirmed that the absorption of the olefin near 1640 cm ^-1 had disappeared, and the reaction was terminated at this point. For the purpose of stabilizing the reaction product, 100 μl of benzothiazole was added, followed by concentration under reduced pressure at 60 ° C. or lower in vacuo to obtain the desired product.

When the structure of the thus obtained adhesiveness-imparting agent was examined by NMR in the same manner as in Production Examples 8, 9, and 10, about 3 epoxy groups and about 3 SiH
It was confirmed that the compound had a group. If the number of SiH groups per unit weight is calculated based on this, 0.365 mo
1/100 g. Examples 1 to 10 Components of (A) obtained in Production Examples 6 to 8, (B) obtained in Production Examples 1 to 5, various Pt catalyst solutions as representatives of Component (C), Production Examples 9 to 11 After blending and curing using the component (D) obtained in the above and other compounds, various properties were evaluated. However, the Si component (A)
H group: alkenyl group of component (B): Pt content of component (C) = 1.1: 1.0: 5 × 10 ⁻⁴ (molar ratio). Table 2 shows the formulation and evaluation results.
It was shown to. The amount of the component (D) used in the table is [(A)
Component + (B) component] as 100 parts by weight.
The amount of the component (E) used is described in terms of a molar ratio to the Pt content of the component (C).

Test and Evaluation Methods 1) Gelation time test method: A part of the mixture was placed on a gelation tester (manufactured by Nissin Kagaku Co., Ltd.) and snap-up time (at rubber elasticity) was measured at 120 ° C. Time until it becomes). 2) Dumbbell tensile test method: The mixture was defoamed by centrifugation, poured into a Teflon mold so as to form a uniform sheet having a thickness of about 2 mm, and defoamed again at room temperature under reduced pressure. A cured product was prepared under predetermined curing conditions (in an oven).
A No. 3 dumbbell according to JIS K6301 was punched out of the sheet of the cured product, and a tensile test was performed at a tensile speed of 200 mm / min.

M ₅₀ (Kg / cm ² ): strength at 50% elongation (modulus) M ₁₀₀ (Kg / cm ² ): strength at 100% elongation (modulus) TB (Kg / cm ² ): breaking strength EB (%): Elongation at break 3) Adhesion evaluation method: Place the centrifugally defoamed compound in an oval shape about 5 mm thick on various substrates (glass, aluminum, mortar) and cure under predetermined curing conditions I let it. After returning the temperature to room temperature, the cured product is peeled off from the substrate by applying a peeling force laterally while pressing it from above with a finger. At this time, those that peeled off at the interface were evaluated as x, those that caused mixed destruction were evaluated as △, and those that completely cohesively fractured were evaluated as ○. 4) Thickening rate (%) Thickening rate of the formulation at room temperature after storage for 2 weeks.

Comparative Examples 1 and 2 The same procedures as in Examples 2 and 10 were carried out except that the component (D) was not used. The evaluation results are also shown in Table 2.

[0087]

[Table 2]

Examples 11 to 16 The following raw materials were further added to the compounding system of Comparative Example 2 and kneaded three times with three paint rolls to obtain a composition for a sealing material. (The blending system of Comparative Example 2 is described as 100 parts by weight) CCR (calcium carbonate): Shiraishi Industry Co., Ltd .: 100 parts by weight Polybutene OH: Idemitsu Oil Co., Ltd .: 90 parts by weight Irganox 1010: Ciba Geigy: 1 part by weight Carbon black # 30: Mitsubishi Chemical Co., Ltd .: 5 parts by weight Titanium oxide R-8200: Ishihara Sangyo Co., Ltd .: 7 parts by weight In addition to these compositions, various (D) components (described in Table 3)
Was uniformly mixed, a cured product was prepared, and various characteristics were evaluated. Table 3 shows the formulation and evaluation results.
The procedure was the same as above except for the glass / aluminum H-type tensile properties.

Test and Evaluation Methods Glass / Aluminum H-type tensile test: According to the preparation of JIS A5758 durability test specimens, the composition was filled and cured under predetermined curing conditions, and then the tensile speed was 50 mm / min.
A tensile test was performed. Comparative example 3 Except not using (D) component, it carried out similarly to Examples 11-16. The evaluation results are also shown in Table 3.

[0090]

[Table 3]

Examples 17 to 21 The glass / aluminum H-type samples prepared in Examples 11 to 15 were subjected to a Sunshine Carbon Bon Arc Weather Meter (120 minutes cycle, spray 18 minutes) for 2000 hours.
After performing the test of r, when the tensile test was performed again,
All samples showed cohesive failure.

[0092]

As is clear from the results of Examples 1 to 21, the curable composition and the sealing material of the present invention are:
(1) high weather resistance, (2) high heat resistance, (3) fast curing,
It is understood that the material is an excellent material having (4) low moisture permeability, (5) adhesiveness with inorganic and organic materials, and (6) one-pack stability.

A material which can be suitably used for various applications by utilizing these characteristics. For example, sealing material applications such as glass sealing material applications, multilayer glass sealing material applications, automotive and electric sealing material applications, and various elastic adhesive applications that can be widely and suitably used and make use of their adhesiveness. It is also suitable for use as a sealant for electric and electronic parts utilizing saturated hydrocarbon-based electrical insulation. In addition, it can be a suitable material as a base resin such as a paint or an adhesive.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-152164 (JP, A) JP-A-4-41562 (JP, A) JP-A-6-116368 (JP, A) JP-A-6-116368 200123 (JP, A) JP-A-4-33945 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C09K 3/10 C08G 59/40

Claims (5)

(57) [Claims] 1. A curable composition comprising the following components (A), (B), (C) and (D) as essential components: (A) a molecular weight containing at least two hydrosilyl groups in a molecule (B) a saturated hydrocarbon polymer having at least one alkenyl group in the molecule and having a molecular weight of 100,000 or less, (C) a hydrosilylation catalyst, (D) an epoxy group, Less of hydroxyl and carboxyl groups
At least one polar functional group and an alkenyl group or hydroxy group;
An adhesion-imparting agent comprising a compound having both of a ril group, and
And / or curing for epoxy resin and non-amine type epoxy resin
Imparting agent consisting of a mixture of agents 2. The curable composition according to claim 1, wherein the total amount of the repeating units derived from isobutylene in the polymer of the component (B) is 50% by weight or more. 3. A sealing material comprising the following components (A), (B), (C) and (D) as essential components: (A) a molecule containing at least two hydrosilyl groups in a molecule and having a molecular weight of 30,000 (B) a saturated hydrocarbon polymer containing at least one alkenyl group in the molecule and having a molecular weight of 100,000 or less (C) a hydrosilylation catalyst (D) an epoxy group, a hydroxyl group, Low in carboxyl groups
At least one polar functional group and an alkenyl group or hydroxy group;
An adhesion-imparting agent comprising a compound having both of a ril group, and
And / or curing for epoxy resin and non-amine type epoxy resin
Imparting agent consisting of a mixture of agents 4. The sealing material according to claim 3, wherein the total amount of repeating units derived from isobutylene in the polymer (B) is 50% by weight or more. 5. The sealing material according to claim 4, further comprising a storage stability improver as an essential component (E).